JP2003252655A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an interlayer for laminated glass which is good in proper ties of heat insulation and sound insulation. <P>SOLUTION: The inter layer is composed of a layer A and a layer B, the layer A consists of a polyvinyl acetal (PVAc) resin P, a plasticizer W, and ITO particles, and the layer B consists of the PVAc resin Q and the plasticizer X. The ITO particles are ≤80 nm in a mean particle diameter, the number of particles ≥100 nm in particle diameter is ≤1 per μm<SP>2</SP>. The particles are contained by 0.01-3.0 pts.wt to 100 pts.wt. PVAc resin P. The PVAc resin Q is composed of a PVAc resin R of a mean polymerization degree of 1,000-3,000 and the PVAc resin S of a mean polymerization degree of 3,000-5,000 which is ≥1,500 in a mean polymerization degree than that of PVAc resin R. The degree of acetalization is 60-85 mol%, the amount of the acetyl group is 8-30 mol%, and their total are ≥75 mol%. The cloud point of the solution in which the 8 pts.wt. PVAc resin Q is dissolved into the 100 pts.wt. plasticizer X, is ≤50°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat insulating property, a sound insulating property,
Electromagnetic wave transparency, penetration resistance, moisture resistance, transparency, particularly good haze, and has an appropriate adhesive force with glass,
The present invention relates to a laminated glass interlayer film and a laminated glass that can be obtained at low cost.

[0002]

2. Description of the Related Art Conventionally, laminated glass is safe because it does not scatter glass fragments even if it is damaged by an external impact, and therefore it is safe to use, for example, window glass for vehicles such as automobiles, aircraft and buildings. Widely used in.

As the laminated glass, for example, an interlayer film for laminated glass (hereinafter, also referred to as an interlayer film) made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized by adding a plasticizer is provided between at least a pair of glasses. Examples include those that are interposed and integrated.
The interlayer film made of polyvinyl butyral resin plasticized by the addition of the plasticizer has excellent adhesiveness to glass,
It has strong tensile strength and high transparency,
The laminated glass obtained by using such an interlayer film is particularly suitable as a window glass for vehicles.

In recent years, laminated glass is strongly required to have sound insulation and heat insulation in addition to safety. Sound insulation is required, for example, in window glass for automobiles, window glass for buildings, and the like that generate wind noise and engine vibration noise during high-speed traveling.

The sound insulation property is generally indicated as a transmission loss amount for each frequency. According to JIS A 4708, the transmission loss amount for frequencies of 500 Hz or more shown by the solid line in FIG. There is.

As shown by the wavy line in FIG. 1, the sound insulation of the glass plate is remarkably lowered by the coincidence effect in the frequency region around 2000 Hz, but as shown by the equal loudness curve, Hearing is 1000-6
Since it shows very high sensitivity in the frequency range of 000 Hz,
It is extremely important in soundproofing to eliminate the decrease in sound insulation due to the coincidence effect. The coincidence effect is a phenomenon in which when a sound wave is incident on a glass plate, a transverse wave propagates on the glass surface due to the rigidity and inertia of the glass plate and the transverse wave and the incident sound wave resonate, causing a sound transmission. For example, the valley portion of the wavy line in FIG. 1 indicates a decrease in sound insulation due to the coincidence effect.

The conventional laminated glass is excellent in preventing scattering of broken pieces, but like the glass plate, there is a problem that the sound insulating property is lowered due to the coincidence effect in the frequency region centering on 2000 Hz. Therefore, in order to improve the sound insulation of the laminated glass, it is necessary to reduce the coincidence effect by increasing the minimum value of the transmission loss due to the coincidence effect (hereinafter, also referred to as TL value).

As methods for increasing the TL value, various methods such as increasing the mass of laminated glass, making glass into multiple layers, subdividing the glass area, and improving the glass plate supporting method have been proposed. There is. However, none of these methods has a sufficient effect, resulting in a high cost.

Further, since laminated glass may be exposed to a wide range of temperature changes from low temperature to high temperature due to environmental changes and the like, good sound insulation is required in a wide temperature range, but especially window glass for buildings, etc. The laminated glass used for is required to have excellent sound insulating properties near room temperature, that is, the temperature at which the sound insulating property has a maximum value is near room temperature, and the maximum sound insulating property is large. The temperature at which the sound insulation has the maximum value can be obtained by plotting the TL value against the temperature.

On the other hand, for example, in the conventional laminated glass using the interlayer film for laminated glass made of plasticized polyvinyl butyral resin, the temperature at which the sound insulating property has the maximum value is higher than room temperature, and the sound insulating property is around room temperature. There was a problem that was not good. In addition, when the sound insulation is attempted to be increased, the intermediate film becomes soft, and there is a problem that when the laminated glass is used, plate displacement and foaming occur.

In order to solve the above problem, Japanese Patent Laid-Open No. 2001-2001
-316140 discloses an interlayer film made of a mixture of polyvinyl acetal resin having a specific viscosity average degree of polymerization, a mixture of polyvinyl acetal resins having a specific degree of acetalization and an amount of acetyl groups, and an interlayer film and a laminated glass. ing.

Such an interlayer film and laminated glass should impair the basic properties required for the laminated glass such as transparency, weather resistance, impact energy absorption and adhesiveness with glass, and the moldability and handleability of the interlayer film. Without, the coincidence effect is mitigated to prevent a decrease in the TL value, excellent sound insulation is stably exhibited over a wide temperature range for a long period of time, and proper film physical properties prevent plate misalignment and foaming when used as a laminated glass. However, there is a problem in that the heat shield property is poor.

Among the light rays, infrared rays having a wavelength of 780 nm or more have an energy amount of about 10 as compared with ultraviolet rays.
Although it is as small as about%, it is generally called a heat ray because it has a large thermal action and is absorbed by a substance to cause a temperature rise. Therefore, for example, in order to suppress the temperature rise inside the automobile, it is sufficient to enhance the heat shielding properties of the windshield and the side glass of the automobile so that infrared rays can be shielded. As a glass plate capable of blocking infrared rays, for example, a heat ray-cut glass or the like is already on the market.

The above-mentioned heat ray-cut glass is one in which a multi-layer coating layer of metal / metal oxide is formed on the surface of a glass plate by metal vapor deposition, sputtering or the like.
Since the coating layer is weak against external scratches and has poor chemical resistance, for example, an interlayer film made of plasticized polyvinyl butyral resin or the like is laminated to form a laminated glass.

However, in such a laminated glass, (a) it is expensive, (b) the transparency (visible light transmittance) is low because the multilayer coating layer is thick, and (c) the multilayer coating layer and the intermediate film. There is a problem in that the adhesiveness of the product deteriorates and the interlayer film peels or whitens, and (d) it impedes the transmission of electromagnetic waves and interferes with the communication functions of mobile phones, car navigation systems, garage openers, automatic cash collection, etc. It was

In order to solve such problems, for example, Japanese Examined Patent Publication No. 61-52093 and Japanese Unexamined Patent Publication No. 64-36.
Japanese Patent No. 442 or the like proposes a laminated glass in which a thin film coating or vapor-deposited polyester film of a metal and / or a metal oxide is laminated between plasticized polyvinyl butyral resin sheets. However, these heat ray-reflecting laminated glasses not only cause peeling at the interface due to insufficient adhesion between the plasticized polyvinyl butyral resin sheet and the polyester film,
Electromagnetic wave transparency, workability, workability in the communication wavelength range,
There were problems such as insufficient productivity.

On the other hand, for the purpose of imparting heat insulating properties to the interlayer film, Japanese Patent Laid-Open No. 8-259279 proposes a laminated glass in which fine particles of a heat insulating inorganic substance are dispersed in the interlayer film. There is. It can be expected that the temperature rise of vehicles and buildings can be suppressed by blocking infrared rays with these fine particles to improve heat insulation.

However, in a laminated glass in which fine particles of a heat insulating inorganic substance such as metal and / or metal oxide are dispersed in an intermediate film, deterioration of haze becomes a problem. This deterioration of haze is largely controlled by the particle size of the heat insulating inorganic substance in the interlayer film, and when the particle size is large, the haze also becomes large.

Therefore, Japanese Patent No. 2715859 discloses a technique in which the particle size of the primary particles is regulated. However, even if the particle size of the primary particles or the particle size in the dispersion liquid is controlled, heat is generated during film formation. During the kneading with the resin, the particles agglomerate, and the particle size in the interlayer film becomes larger than the particle size of the primary particles and the particle size of the dispersion liquid. That is, in the production of the interlayer film, it is necessary not only to regulate the particle diameter of the primary particles and the dispersion liquid but also to regulate the particle diameter of the heat insulating inorganic substance in the interlayer film that directly affects the haze.

Further, recently, a mold in which the edge portion of the windshield of an automobile is exposed has become common, but when the laminated glass is exposed to high humidity, the film becomes white and deteriorates due to moisture absorption (whitening due to moisture absorption). ) Occurs. If the edge cross section of the laminated glass is exposed, it is directly visible to the human eye, which causes a great aesthetic problem. Therefore, there is a problem that it is necessary to improve the moisture resistance and suppress the whitening by moisture absorption.

Since laminated glass typified by laminated glass for automobiles is also required to have penetration resistance, even if only haze is good, it is not sufficient as a laminated glass, and the adhesive strength with glass can be adjusted appropriately. Needed. A dispersant is required to evenly disperse the fine particles of the heat insulating inorganic substance in the interlayer film, but this dispersant affects the adhesive force between the glass and the interlayer film, and Is not obtained,
There are problems that peeling occurs, penetration resistance decreases, and the adhesive strength may change over time due to bleeding of the dispersant.

[0022]

DISCLOSURE OF THE INVENTION According to the present invention, heat insulation, sound insulation, electromagnetic wave transparency, penetration resistance, moisture resistance, transparency, particularly haze are excellent, and an appropriate adhesive force with glass is obtained. It is an object of the present invention to provide an interlayer film for laminated glass and a laminated glass which can be obtained at low cost.

[0023]

The present invention 1 has a laminated structure including at least three layers of two layers (A) and (B) sandwiched between the layers (A). An interlayer film for laminated glass, wherein the (A) layer comprises a polyvinyl acetal resin (P), a plasticizer (W) and tin-doped indium oxide particles, and the (B) layer comprises a polyvinyl acetal resin (Q). And the plasticizer (X), the tin-doped indium oxide particles have an average secondary aggregate particle diameter of 80 nm or less in the (A) layer, and particles having a secondary aggregate particle diameter of 100 nm or more are ) 1 layer / μm in layer
^The polyvinyl acetal resin (P) 10 is dispersed in the layer (A) so as to have a density of ² or less.
The polyvinyl acetal resin (Q) is contained in an amount of 0.01 to 3.0 parts by weight based on 0 parts by weight, and the polyvinyl acetal resin (Q) has a viscosity average degree of polymerization of 1000 to 3000 and the polyvinyl acetal resin. (R) is a polyvinyl acetal resin (S) having a viscosity average degree of polymerization of 1500 or more and a viscosity average degree of polymerization of 3000 to 5000, and an acetalization degree of 60 to 85 mol%. The amount of acetyl groups is 8 to 30 mol%, the sum of the degree of acetalization and the amount of acetyl groups is 75 mol% or more, and 100 parts by weight of the plasticizer (X) is mixed with 8 parts by weight of the polyvinyl acetal resin (Q). This is an interlayer film for laminated glass in which the cloud point of the dissolved solution is 50 ° C. or lower.

The present invention 2 is an interlayer film for laminated glass having a laminated structure having at least three layers of (A) layer of two layers and (C) layer sandwiched between the (A) layer. There
The (A) layer comprises a polyvinyl acetal resin (P), a plasticizer (W) and tin-doped indium oxide particles,
The (C) layer comprises a polyvinyl acetal resin (T) and a plasticizer (Y), and the tin-doped indium oxide particles have an average secondary aggregate particle size of 8 in the (A) layer.
Particles having a secondary aggregate particle size of 0 nm or less and a particle size of 100 nm or more are dispersed in the (A) layer so as to have a density of 1 particle / μm ² or less, and the polyvinyl acetal is contained in the (A) layer. 0.0 per 100 parts by weight of resin (P)
1 to 3.0 parts by weight is contained, and the plasticizer (Y)
Is selected from the group consisting of triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, triethylene glycol di-n-heptanoate, and tetraethylene glycol di-n-heptanoate. The layer (C) is an interlayer film for laminated glass, which has a temperature dependence of the loss tangent obtained from dynamic viscoelasticity that is 30 ° C. or lower as the maximum value on the lowest temperature side. is there. The present invention is described in detail below.

The interlayer film for laminated glass of the present invention 1 and the invention 2 (hereinafter, also referred to as an intermediate film) is sandwiched between at least two layers (A) and (A) (B). ) Layer or (C) layer. As the above-mentioned laminated structure, specifically, for example,
(A) layer / (B) layer / (A) layer, (A) layer / (C) layer /
(A) layer, (A) layer / (B) layer / (A) layer / (A) layer,
Examples include (A) layer / (C) layer / (A) layer / (A) layer. By stacking a layer having a sound insulation property and a layer having a heat insulation property, while suppressing an adverse effect such as a decrease in strength,
The temperature dependences of the sound insulation properties of the respective layers can be overlapped, and an interlayer film having both good sound insulation properties and heat insulation properties in a wide temperature range can be obtained inexpensively and easily. Specifically, for example, in order to improve the sound insulation on the low temperature side of the interlayer film, the glass transition temperature (Tg) is lowered by increasing the amount of the plasticizer added to the (B) layer or the (C) layer. For example, a method of shifting the sound insulation of the (B) layer or the (C) layer to the low temperature side by shifting to the low temperature side can be adopted.

The film thickness of the intermediate film of the invention 1 and the invention 2 is not particularly limited, but in view of the minimum penetration resistance and weather resistance required for the laminated glass, the preferable lower limit is 0.3 mm and the upper limit is 0. It is 0.8 mm.

The (A) layer in the interlayer films of the first and second aspects of the present invention comprises a polyvinyl acetal resin (P), a plasticizer (W) and tin-doped indium oxide particles (hereinafter referred to as ITO).
(Also called). Although the polyvinyl acetal resin (P) is not particularly limited, for example,
Polyvinyl butyral resin is preferably used. The use of the polyvinyl butyral resin makes the resulting interlayer film excellent in transparency, weather resistance, adhesion to glass and the like. The polyvinyl acetal resin (P) may be blended in an appropriate combination according to the required physical properties, and a co-polyvinyl acetal obtained by combining aldehydes during acetalization and acetalization. It may be a resin.
The molecular weight and molecular weight distribution of the polyvinyl acetal resin (P) are not particularly limited, but the degree of acetalization is generally 40 to 85%, and the preferable lower limit thereof is 60% and the upper limit thereof is 75%.

The polyvinyl butyral resin can be obtained by acetalizing a polyvinyl alcohol resin with an aldehyde. The polyvinyl alcohol resin is generally obtained by saponifying polyvinyl acetate, and a polyvinyl alcohol resin having a saponification degree of 80 to 99.8 mol% is generally used. The preferred lower limit of the viscosity average degree of polymerization of the polyvinyl alcohol resin is 200, and the upper limit thereof is 3000. If it is less than 200, the penetration resistance of the obtained laminated glass is lowered. Three
When it exceeds 000, the moldability of the resin film becomes poor, and the rigidity of the resin film becomes too high, resulting in poor processability. A more preferable lower limit is 500 and an upper limit is 2000. The viscosity average degree of polymerization and the degree of saponification of the polyvinyl alcohol resin can be measured, for example, according to JIS K 6726 “Polyvinyl alcohol test method”.

The aldehyde is not particularly limited,
For example, an aldehyde having a carbon number of 1 to 10 can be mentioned,
More specifically, for example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde. , Benzaldehyde and the like. Among them, n-butyraldehyde, n-hexylaldehyde, n-valeraldehyde and the like are preferable. More preferably, it is butyraldehyde having 4 carbon atoms.

The above-mentioned plasticizer (W) is not particularly limited, and examples thereof include known plasticizers generally used as plasticizers for interlayer films. Examples thereof include monobasic organic acid esters and polybasic organic acids. Organic plasticizers such as organic acid esters; phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid are preferably used. These plasticizers may be used alone or in combination of two or more, and may be used in consideration of compatibility and the like depending on the type of the polyvinyl acetal resin (P).

The monobasic organic acid ester is not particularly limited, and examples thereof include glycols such as triethylene glycol, tetraethylene glycol or tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid and heptanoic acid. , Heptyl acid, n-octylic acid, 2
Examples thereof include glycol-based esters obtained by reaction with a monobasic organic acid such as ethylhexylic acid, pelargonic acid (n-nonyl acid) or decyl acid. Among them, one of triethylene glycol such as triethylene glycol dicaproic acid ester, triethylene glycol di-2-ethylbutyric acid ester, triethylene glycol di-n-octyl acid ester, and triethylene glycol di-2-ethylhexylic acid ester. Basic organic acid esters are preferably used.

The polybasic organic acid ester is not particularly limited, and examples thereof include polybasic organic acids such as adipic acid, sebacic acid, and azelaic acid, and linear or branched alcohols having 4 to 8 carbon atoms. Examples thereof include esters obtained by the reaction with, and among these, dibutyl sebacate ester, dioctyl azelaate ester, dibutyl carbitol adipate ester, and the like are preferably used.

The organophosphate plasticizer is not particularly limited, and examples thereof include triethylene glycol diethyl butyrate, triethylene glycol diethyl hexoate, triethylene glycol dibutyl sebacate, tributoxyethyl phosphate, isodecylphenyl phosphate, Triisopropyl phosphate and the like can be mentioned. Among them, triethylene glycol diethyl butyrate,
Triethylene glycol diethyl hexoate, triethylene glycol dibutyl sebacate and the like are preferable.

The compounding amount of the plasticizer (W) is not particularly limited, but the preferable lower limit of the compounding amount is 20 parts by weight and the upper limit thereof is 100 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin (P). If the amount is less than 20 parts by weight, IT
O particles may not be sufficiently dispersed, and the penetration resistance may decrease. If it exceeds 100 parts by weight, bleed-out may occur, the transparency and adhesiveness of the (A) layer may deteriorate, and the optical strain of the obtained laminated glass may increase. A more preferred lower limit is 30 parts by weight and an upper limit is 60 parts by weight.

The layer (A), which contains ITO particles, has an infrared ray cutting effect and a heat shielding property.
The ITO particles have an average secondary agglomerated particle diameter of 80 nm or less in the (A) layer. If it exceeds 80 nm,
Scattering of visible light due to ITO particles becomes remarkable, (A)
The transparency of the layer may be impaired. As a result, the haze (fogging value) of the laminated glass deteriorates, and it becomes impossible to obtain the high degree of transparency required for windshields of automobiles.

The ITO particles have a secondary aggregate particle diameter of 100.
Particles having a size of nm or more are dispersed in the layer (A) so as to have a density of 1 particle / μm ² or less. That is,
When the (A) layer is photographed and observed with a transmission electron microscope,
No ITO particles having a particle size of 100 μm or more are observed, or if observed, if ITO particles having a particle size of 100 μm or more are placed in the center of a frame of 1 μm ² , the 1 μm
ITO particles having a particle diameter of 100 μm or more are dispersed in a frame of m ² so that no other particles can be observed. Thereby, when it is made into a laminated glass, it has a low haze, excellent transparency, and a high heat-shielding property over the entire (A) layer, and further, the adhesive force between the glass and the interlayer film can be adjusted. It also has excellent penetration resistance. In addition,
Observation with a transmission electron microscope is H-7 manufactured by Hitachi, Ltd.
Accelerating voltage 10 using a 100FA transmission electron microscope
This can be done by shooting at 0 kV.

The ITO particles are contained in the layer (A) in an amount of 0.01 to 3.0 parts by weight based on 100 parts by weight of the polyvinyl acetal resin (P). If the amount is less than 0.01 part by weight, the infrared ray cutting effect may be insufficient.
If it exceeds 3.0 parts by weight, the transparency to visible light may decrease and the haze may increase.

When an additive having a size equal to or larger than the visible light wavelength is added to a transparent resin such as an interlayer film which requires a high visible light transmittance, visible light is usually strongly scattered by the above-mentioned additive. There is concern about a decrease in visible light transmittance and an increase in haze. Since the ITO particles are uniformly dispersed in the state of nano-scale ultrafine particles much smaller than the visible light wavelength and have infrared absorption, even if added to the inside of the (A) layer, The haze is extremely small because the transparency is maintained without causing scattering, and the layer (A) has a function of absorbing infrared rays. Further, since the (A) layer has electromagnetic wave transparency without causing reflection even in the communication wavelength band,
Unlike conventional heat-reflecting laminated glass obtained by vapor deposition or coating, it does not hinder the communication function.

The layer (A) may contain an adhesive strength modifier, if necessary. Examples of the adhesive strength modifier include alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids, modified silicone oil, and the like. The organic acid is not particularly limited, and examples thereof include carboxylic acids such as octylic acid, hexylic acid, butyric acid, acetic acid, and formic acid. The inorganic acid is not particularly limited, and examples thereof include hydrochloric acid and nitric acid. The alkali metal salt and the alkaline earth metal salt are not particularly limited, and examples thereof include salts of potassium, sodium, magnesium and the like.

Among the alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids mentioned above, alkali metal salts and alkaline earth metal salts of organic acids having 2 to 16 carbon atoms are preferable, and more preferable are the carbon number. The potassium and magnesium salts of 2 to 16 carboxylic acids.

The potassium salt and magnesium salt of the carboxylic acid having 2 to 16 carbon atoms are not particularly limited,
For example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, potassium 2-ethylbutanoate, 2
-Magnesium ethylhexanoate, potassium 2-ethylhexanoate and the like are preferable. These may be used alone or in combination of two or more.

The preferable lower limit of the compounding amount of the alkali metal salt or alkaline earth metal salt of the organic acid or the inorganic acid is 0.10 with respect to 100 parts by weight of the polyvinyl acetal resin (P).
001 parts by weight, the upper limit is 0.5 parts by weight. 0.001
If the amount is less than the weight part, the adhesive strength of the peripheral part may be reduced in a high humidity atmosphere. If it exceeds 0.5 parts by weight, the adhesive strength may be too low and the transparency of the film may be lost. A more preferred lower limit is 0.01 part by weight and an upper limit is 0.1.
2 parts by weight.

The modified silicone oil is not particularly limited, and examples thereof include epoxy modified silicone oil, ether modified silicone oil, ester modified silicone oil, amine modified silicone oil, and carboxyl modified silicone oil. These may be used alone or in combination of two or more. These modified silicone oils are generally obtained by reacting a polysiloxane with a compound to be modified.

The preferred lower limit of the molecular weight of the modified silicone oil is 800, and the upper limit thereof is 5000. If it is less than 800, localization on the surface may be insufficient. Fifty
If it exceeds 00, the compatibility with the resin may decrease, and the film may bleed out to reduce the adhesive strength with the glass. A more preferable lower limit is 1500 and an upper limit is 4000.

The preferred lower limit of the amount of the modified silicone oil blended is 0.01 parts by weight, and the upper limit is 0.2 parts by weight, per 100 parts by weight of the polyvinyl acetal resin (P). If it is less than 0.01 part by weight, the effect of preventing whitening due to moisture absorption may be insufficient. If it exceeds 0.2 parts by weight, the compatibility with the resin may decrease, and bleeding out may occur on the film surface, resulting in a decrease in the adhesive force between the resin and the glass. A more preferred lower limit is 0.03 parts by weight and an upper limit is 0.1.
Parts by weight.

The layer (A) may further include, if necessary.
Antioxidants to prevent deterioration due to heat in the extruder, UV absorbers and light stabilizers to improve weather resistance and light resistance, surfactants, flame retardants, antistatic agents, moisture resistant agents, heat rays Additives such as a reflector and a heat ray absorber may be added.

Although the above-mentioned antioxidant is not particularly limited, for example, phenol-based ones are preferable. Specifically, for example, the product name "Sumirider BHT" manufactured by Sumitomo Chemical Co., Ltd. or the product name manufactured by Ciba Geigy Co., Ltd. “Irganox 1010” and the like can be mentioned.

The ultraviolet absorber is not particularly limited, but for example, a benzotriazole-based one is preferable. Specifically, for example, trade names "Tinuvin P", "Tinuvin 320", and "Tinuvin 32" manufactured by Ciba-Geigy are available.
6 ”,“ Tinuvin 328 ”and the like.

Although the light stabilizer is not particularly limited, for example, hindered amine-based light stabilizers are preferable, and specific examples thereof include "Adeka Stab LA-57" manufactured by Asahi Denka Kogyo Co., Ltd.

The above-mentioned surfactant is not particularly limited,
Examples thereof include sodium laurate and alkylbenzene sulfonic acid.

The layer (A) is generally prepared by adding a dispersion obtained by uniformly dispersing ITO particles in an organic solvent with a dispersant to an adhesive resin containing a plasticizer and melt-kneading the mixture.
It can be formed by a method of forming a film. The main dispersion medium used for the dispersion is not particularly limited, and examples thereof include a plasticizer of the same kind as the plasticizer used, and a dispersion stabilizer such as an organic and inorganic surfactant generally used as a dispersant for inorganic fine particles. Among them, a plasticizer of the same kind as the plasticizer used in the (A) layer is preferable. The dispersion stabilizer is not particularly limited, and specific examples thereof include a sulfuric acid ester compound, a phosphoric acid ester compound, a polycarboxylic acid salt, and a polyhydric alcohol type surfactant.

The preferred lower limit of the blending amount of the main dispersion medium is
The amount of the ITO particles is 0.001 part by weight, and the upper limit is 5 parts by weight. When it is less than 0.001 part by weight,
The effect may not be expected. If it exceeds 5 parts by weight,
Foaming may occur during film formation and during production of laminated glass, or the adhesive force between the interlayer film and the glass may increase excessively. A more preferred lower limit is 0.05 parts by weight and an upper limit is 1.0.
Parts by weight.

During the melt-kneading, the haze can be further improved by adding a chelating agent and / or a compound having at least one or more carboxyl groups to the kneaded product. The chelating agent has a function of coordinating with the ITO particles to prevent aggregation of the ITO particles, and the compound having one or more carboxyl groups has a high dispersibility and uniformly disperses the ITO particles to give a haze. It is thought that the above can be improved.

The chelating agent is not particularly limited,
Examples thereof include EDTAs and β-diketones. Of these, β-diketones are preferable because they have good compatibility with plasticizers and resins, and acetylacetone is particularly preferable. In addition to acetylacetone, benzoyltrifluoroacetone, dipivaloylmethane or the like may be used.

The preferable lower limit of the amount of the above chelating agent to be compounded is 0.0 based on 1.0 part by weight of the ITO particles in the kneaded product.
01 parts by weight, the upper limit is 2 parts by weight. If it is less than 0.001 part by weight, the effect may not be expected. If it exceeds 2 parts by weight, foaming may occur during film formation and during production of laminated glass. A more preferred lower limit is 0.01 part by weight and an upper limit is 1 part by weight.

The compound having one or more carboxyl groups is not particularly limited, and examples thereof include an aliphatic carboxylic acid, an aliphatic dicarboxylic acid, an aromatic carboxylic acid, an aromatic dicarboxylic acid and a hydroxy acid. Specific examples thereof include benzoic acid, phthalic acid, salicylic acid and ricinoleic acid. Of these, aliphatic carboxylic acids having 2 to 18 carbon atoms are preferable, and aliphatic carboxylic acids having 2 to 10 carbon atoms are more preferable. Specific examples include acetic acid, propionic acid, n-butyric acid, 2ethylbutyric acid, n-hexanoic acid, 2ethylhexanoic acid, and n-octanoic acid.

The preferable lower limit of the compounding amount of the compound having one or more carboxyl groups is 0.001 part by weight, and the upper limit is 2 parts by weight, relative to 1.0 part by weight of the ITO particles in the kneaded product. If it is less than 0.001 part by weight, the effect may not be expected. If it exceeds 2 parts by weight, the (A) layer may turn yellow, and the adhesive force between the glass and the (A) layer may be impaired. A more preferred lower limit is 0.01 part by weight and an upper limit is 1 part by weight.

The layer (A) has excellent heat-shielding properties and transparency when it is made into a laminated glass by controlling the ITO content and dispersion state in the film, and has an adhesive force with glass. Is adjustable, has excellent penetration resistance, and has electromagnetic wave transparency. Further, the layer (A) can be obtained by the same manufacturing method as that for a normal interlayer film by using ITO particles dispersed in a plasticizer, and the layer (A) itself has an infrared ray cutting effect. A laminated glass having an infrared ray cutting effect can be manufactured by the same manufacturing method as that for ordinary laminated glass, and is excellent in workability, workability, and productivity.

The (B) layer in the interlayer film of the invention 1 is 2
It is sandwiched between the (A) layers and mainly imparts sound insulation to the interlayer film of the present invention 1. Above (B)
The layers are polyvinyl acetal resin (Q) and plasticizer (X)
It consists of and.

The polyvinyl acetal resin (Q) is
It is composed of two kinds of polyvinyl acetal resin (R) and polyvinyl acetal resin (S) having different viscosity average polymerization degrees. The polyvinyl acetal resin (R) and the polyvinyl acetal resin (S) are not particularly limited, but polyvinyl butyral resin is preferably used. The use of the polyvinyl butyral resin makes the resulting interlayer film excellent in transparency, weather resistance, adhesion to glass and the like. The polyvinyl acetal resin (R) may be used alone or in combination of two or more, and the polyvinyl acetal resin (S) may be used alone or in combination of two or more. May be.

The polyvinyl acetal resin (R) has a viscosity average degree of polymerization of 1000 to 3000. When the viscosity average degree of polymerization is 1,000 to 3,000, the obtained intermediate film exhibits good sound insulation in a wide temperature range, especially at low temperatures, but the physical properties of the film become soft. Etc. are likely to occur. On the other hand, the polyvinyl acetal resin (S) has a viscosity average degree of polymerization of 3000.
~ 5000. When it is 3,000 to 5,000, the resulting intermediate film has a hard film physical property and an effect of preventing plate misalignment and foaming when it is made into a laminated glass appears, but viscosity at high temperature becomes high and resin moldability becomes poor. Become.

The above polyvinyl acetal resin (Q) is
Polyvinyl acetal resin (R) and polyvinyl acetal resin (S) having a difference in viscosity average degree of polymerization of 1500 or more
It is a mixture of and. When it is less than 1500, the layer (B) may not have sufficient film physical properties. When the polyvinyl acetal resin (Q) is composed of a combination of the polyvinyl acetal resin (R) and the polyvinyl acetal resin (S), the layer (B) has excellent sound insulation in a wide temperature range, and
Since it has appropriate film physical properties, it is possible to prevent the plate from slipping and foaming when it is used as a laminated glass.

The polyvinyl acetal resin (R) and the polyvinyl acetal resin (S) are prepared, for example, by keeping an aqueous solution of a polyvinyl alcohol resin dissolved in hot water at a predetermined temperature and then adding an aldehyde and a catalyst thereto to carry out an acetalization reaction. And then the reaction solution is kept at a high temperature at a predetermined temperature and then undergoes steps such as neutralization, washing with water, and drying to obtain a resin powder.

The polyvinyl alcohol resin is not particularly limited, but the preferable lower limit of the viscosity average degree of polymerization is 5
00 and the upper limit is 5000. If it is less than 500, the strength of the resulting interlayer film may be too weak, and the penetration resistance and impact energy absorption of the laminated glass may be insufficient. If it exceeds 5,000, it may be difficult to mold the resin, and the strength of the resulting intermediate film may become too strong, resulting in insufficient penetration resistance and impact energy absorption when using laminated glass. There is. A more preferable lower limit is 1000.

The aldehyde is not particularly limited,
For example, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, benzaldehyde,
Examples include cinnamaldehyde and the like. These may be used alone or in combination of two or more.

As a method for mixing the polyvinyl acetal resin (R) and the polyvinyl acetal resin (S), for example, a predetermined amount of polyvinyl alcohols having different viscosity average polymerization degrees are mixed, and then an acetalization reaction is performed to perform a mixed polyvinyl acetal resin. And a method of mixing a predetermined amount of polyvinyl acetal resins obtained from polyvinyl alcohols having different viscosity average degree of polymerization, and the like.

The polyvinyl acetal resin (Q) is
The degree of acetalization is 60 to 85 mol%. 60 mol%
If it is less than the above range, the compatibility with the plasticizer is deteriorated, and it may be difficult to add the plasticizer in an amount necessary to secure the penetration resistance of the laminated glass and to exert the sound insulation particularly in a low temperature range. 85
If it exceeds mol%, a long-time reaction may be required to obtain the polyvinyl acetal resin (Q). The preferred lower limit is 63 mol% and the upper limit is 70 mol%.

The polyvinyl acetal resin (Q) is
The amount of acetyl groups is 8 to 30 mol%. When it is less than 8 mol%, the compatibility with the plasticizer is deteriorated, the glass transition temperature of the obtained resin is not sufficiently lowered, and the sound insulation in the low temperature region is not sufficiently obtained. If it exceeds 30 mol%,
Since the reactivity between polyvinyl alcohol and aldehyde is remarkably reduced, the polyvinyl acetal resin (Q) may not be sufficiently obtained. The preferred lower limit is 10 mol% and the upper limit is 24 mol%.

The polyvinyl acetal resin (Q) is
The sum of the degree of acetalization and the amount of acetyl groups is 75 mol% or more. If it is less than 75 mol%, the compatibility with the plasticizer (X) may be insufficient, and the sound insulation in the low temperature range may be insufficient. It is preferably 77 mol% or more.

The polyvinyl acetal resin is composed of a vinyl acetal component and a vinyl alcohol component, and the amount of components such as the degree of acetalization and the amount of acetyl groups is, for example, JIS K 6728 "Polyvinyl butyral test method" or infrared. It can be measured based on an absorption spectrum (IR). In the present specification, the degree of acetalization is the degree of acetalization when the acetal group is counted as two acetalized hydroxyl groups. The viscosity average degree of polymerization of the polyvinyl acetal resin can be measured based on, for example, JIS K 6728 "Polyvinyl butyral test method".

The plasticizer (X) is not particularly limited and may be the same as or different from the plasticizer (W). For example, a monobasic organic acid ester, a polybasic organic acid ester and the like can be used. Organic plasticizers: examples include organic phosphoric acid-based and organic phosphorous acid-based phosphoric acid-based plasticizers. Among them, for example, triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), tri Ethylene glycol di-n-heptanoate (3G7), tetraethylene glycol di-n-heptanoate (4G
7), triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, tetraethylene glycol di-2-ethylbutyrate, tetraethylene glycol di-n-heptanoate, dihexyl adipate, dibenzyl phthalate and the like are preferable. More preferably, 3GO, 3GH, 3G7 and the like. The plasticizers may be used alone or in combination of two or more.

The preferred lower limit of the amount of the plasticizer (X) blended is 30 parts by weight, and the upper limit thereof is 70 parts by weight per 100 parts by weight of the polyvinyl acetal resin (Q). When the amount is less than 30 parts by weight, the polyvinyl acetal resin (Q) may be insufficiently plasticized and the (B) layer may be insufficient in sound insulation. If it exceeds 70 parts by weight, the mechanical strength of the layer (B) is lowered and the impact resistance is lowered,
The adhesive force between the layer (B) and the glass may be insufficient.

The cloud point of a solution prepared by dissolving 8 parts by weight of the polyvinyl acetal resin (Q) in 100 parts by weight of the plasticizer (X) is 50 ° C. or lower. If the temperature exceeds 50 ° C, the compatibility between the polyvinyl acetal resin (Q) and the plasticizer (X) is poor, and it becomes difficult to add the plasticizer (X) in an amount necessary to secure the penetration resistance of the laminated glass. , Sound insulation may not be exhibited especially in a low temperature range. Preferably 30
C. or lower, more preferably 20.degree. C. or lower.

In the present specification, the cloud point means J
It is measured according to IS K 2269 "Testing method for pour point of crude oil and petroleum products and cloud point of petroleum products". Specifically, 8 parts by weight of polyvinyl acetal resin is dissolved in 100 parts by weight of a plasticizer. The solution obtained by
This means the temperature at which part of this solution begins to become cloudy when heated to 0 ° C. or higher and then left in an atmosphere of 10 to 30 ° C. to lower the temperature. The lower this cloud point,
It shows that the resin and the plasticizer have a high compatibility.

As a method for measuring the cloud point, for example,
Examples include a method of visually observing the appearance of the solution, a method of measuring the haze of the solution with a haze meter, and a method of comparing the appearance of the solution with a preliminarily prepared multi-step limit sample for haze and determining the haze.

Similar to the layer (A), the layer (B) may be, for example, an adhesiveness adjusting agent, an antioxidant, an ultraviolet absorber or a light stabilizer, a surfactant, a flame retardant, if necessary. Additives such as an antistatic agent, a moisture resistance agent, a heat ray reflecting agent, and a heat ray absorbing agent may be further added.

The (C) layer in the interlayer film of the second invention is 2
It is sandwiched between the (A) layers and mainly imparts sound insulation to the interlayer film of the second invention. Above (C)
The layer is made of polyvinyl acetal resin (T) and plasticizer (Y)
It consists of and.

The polyvinyl acetal resin (T) is not particularly limited, but for example, polyvinyl butyral resin is preferably used. The use of the polyvinyl butyral resin makes the resulting interlayer film excellent in transparency, weather resistance, adhesion to glass and the like. The polyvinyl acetal resin (T) may be blended in an appropriate combination depending on the required physical properties, and a co-polyvinyl acetal obtained by combining aldehydes during acetalization and acetalization. It may be a resin.

As the polyvinyl acetal resin (T), the difference in the viscosity average degree of polymerization between the polyvinyl alcohol resin (G) and the polyvinyl alcohol resin (G) is 5
Those obtained from the polyvinyl alcohol resin (I) composed of the polyvinyl alcohol resin (H) of 00 or more are preferably used. If the difference in viscosity average degree of polymerization is less than 500, the effect of mixing may not be observed.

The polyvinyl alcohol resin (G), polyvinyl alcohol resin (H), and polyvinyl alcohol resin (I) are not particularly limited, but the preferable lower limit of the viscosity average polymerization degree of the polyvinyl alcohol resin (G) is 500, The upper limit is 3000, and the preferable lower limit of the viscosity average degree of polymerization of the polyvinyl alcohol resin (H) is 3
000 and the upper limit is 5000. The viscosity average degree of polymerization and the degree of saponification of the polyvinyl alcohol resin are, for example, J
It can be measured based on IS K 6726 "Polyvinyl alcohol test method".

The polyvinyl acetal resin (T) has a viscosity average polymerization degree difference of 5 between the polyvinyl acetal resin (U) and the polyvinyl acetal resin (U).
A polyvinyl acetal resin (V) of 00 or more is also preferably used. If the difference in viscosity average degree of polymerization is less than 500, the effect of mixing may not be observed.

The polyvinyl acetal resin (U) and the polyvinyl acetal resin (V) are not particularly limited, but for example, polyvinyl butyral resin is preferably used. The use of the polyvinyl butyral resin makes the resulting interlayer film excellent in transparency, weather resistance, adhesion to glass and the like. The preferable lower limit of the viscosity average degree of polymerization of the polyvinyl acetal resin (U) is 50.
0, the upper limit is 3000, and the preferable lower limit of the viscosity average polymerization degree of the polyvinyl acetal resin (V) is 3000, and the upper limit thereof is 5000.

By using as a raw material a mixture of polyvinyl alcohol resins having different viscosity average degree of polymerization or by using a polyvinyl acetal resin having a different viscosity average degree of polymerization, the polyvinyl acetal resin (T) The temperature range with good sound insulation can be widened. Further, when mixed, the resin having a low degree of polymerization acts like a plasticizer, so that the fluidity of the resin having a high degree of polymerization is lowered at a high temperature to facilitate molding, and the resin having a high degree of polymerization has a low degree of polymerization. Since it is scattered in the resin and acts like a cross-linking point, the mechanical strength is efficiently improved without the fluidity at high temperature becoming too high.

The polyvinyl acetal resin (T) is
The viscosity average degree of polymerization is preferably 1500 or more.
If it is less than 1500, the sound insulation may be insufficient,
In addition, since the mechanical strength is insufficient, the impact resistance of the laminated glass may be poor.

The polyvinyl acetal resin (T) is
The degree of acetalization is preferably 60 to 85 mol%. When it is less than 60 mol%, the compatibility with the plasticizer (Y) becomes poor, and it becomes difficult to add the plasticizer (Y) in an amount necessary for ensuring the penetration resistance of the laminated glass, and particularly in the low temperature range. In some cases, sound insulation may not be exhibited. If it exceeds 85 mol%, a long-time reaction may be required to obtain the polyvinyl acetal resin (T). The preferred lower limit is 63 mol% and the upper limit is 70 mol%.

The polyvinyl acetal resin (T) is
The amount of acetyl groups is preferably 8 to 30 mol%.
When it is less than 8 mol%, the compatibility with the plasticizer (Y) is deteriorated, the glass transition temperature of the obtained resin is not sufficiently lowered, and the sound insulating property in a low temperature region is not sufficiently obtained. When it exceeds 30 mol%, the reactivity between polyvinyl alcohol and an aldehyde is remarkably reduced, so that the polyvinyl acetal resin (T) may not be sufficiently obtained. The preferred lower limit is 10 mol% and the upper limit is 24 mol%.

The above polyvinyl acetal resin (T) is
The sum of the degree of acetalization and the amount of acetyl groups is preferably 75 mol% or more. When it is less than 75 mol%, the compatibility with the plasticizer (Y) may be insufficient, and the sound insulation in the low temperature range may not be sufficient. It is preferably 77 mol% or more.

The above-mentioned plasticizer (Y) includes triethylene glycol di-2-ethylhexanoate (3GO) and tetraethylene glycol di-2-ethylhexanoate (4).
GO), triethylene glycol di-n-heptanoate (3G7), and tetraethylene glycol di-n.
-At least one selected from the group consisting of heptanoate (4G7). The use of 3GO, 4GO, 3G7, and 4G7 facilitates compatibility between sound insulation and heat resistance and moisture resistance.

The cloud point of a solution prepared by dissolving 8 parts by weight of the polyvinyl acetal resin (T) in 100 parts by weight of the plasticizer (Y) is preferably 50 ° C. or lower. Above 50 ° C, polyvinyl acetal resin (T) and plasticizer (Y)
Since it has poor compatibility with, it becomes difficult to add the plasticizer (Y) in an amount necessary to secure the penetration resistance of the laminated glass,
In particular, sound insulation may not be exhibited in a low temperature range.
It is preferably 30 ° C or lower, and more preferably 20 ° C or lower.

It is preferable that the blending amount of the plasticizer (Y) with respect to 100 parts by weight of the polyvinyl acetal resin (T) is 5 parts by weight or more than the blending amount of the plasticizer (W) with respect to 100 parts by weight of the polyvinyl acetal resin (P). . When the difference in the blending amount is less than 5 parts by weight, the polyvinyl acetal resin (T) may be insufficiently plasticized and the (C) layer may be insufficient in sound insulation.

In the layer (C), it is preferable that the temperature showing the maximum value on the lowest temperature side is 30 ° C. or lower in the temperature dependence of the loss tangent obtained from dynamic viscoelasticity. When it exceeds 30 ° C., the layer (C) does not exhibit sufficient flexibility near room temperature, and the laminated glass using the layer (C) may not exhibit sufficient sound insulation around room temperature.

Loss tangent (t
An δ) means the ratio of the storage elastic modulus to the loss elastic modulus that is generally obtained by measuring the dynamic viscoelasticity of a polymer material.
Generally, the temperature at which the loss tangent exhibits the maximum value when the dynamic viscoelasticity measurement is performed while changing the temperature of the polymer material corresponds to Tg, that is, the softening temperature. The temperature showing the maximum value on the lowest temperature side is the lowest temperature at which the loss tangent shows the maximum value when the dynamic viscoelasticity measurement is performed while changing the temperature, and corresponds to the Tg of the (C) layer. It is a thing.

The temperature showing the maximum value on the lowest temperature side is generally obtained by measuring Tg before lamination.
Depending on the combination of the resin and the plasticizer, transfer of the plasticizer between the laminated layers may occur and the Tg measured before lamination does not make sense. In this case, for example, shear is used for dynamic strain. Tg is measured in the state of the laminated body by dynamic viscoelasticity measurement.

The dynamic viscoelasticity measurement using shear for the dynamic strain can be carried out by using a generally-used dynamic viscoelasticity measuring device, and the principle of the measurement is that the strain having a minute vibration is sheared. The elastic modulus is calculated by applying the stress to the sample by the method and detecting the stress which is the response. In the dynamic viscoelasticity measurement using shear for the dynamic strain, the behavior of the loss elastic modulus and the storage elastic modulus is obtained for each layer of the laminate,
The Tg of each layer can be estimated by obtaining the loss tangent from this behavior and setting the temperature at which the loss tangent is maximum to Tg. The frequency of the strain having the microvibration is not particularly limited, but for example, 10 Hz is preferably used in view of easiness of measurement and accuracy.

If necessary, the (C) layer may include, for example, an adhesion control agent, an antioxidant, an ultraviolet absorber or a light stabilizer, and a surface active agent, similarly to the (A) layer and the (B) layer. Additives such as agents, flame retardants, antistatic agents, moisture resistant agents, heat ray reflectors, heat ray absorbers and the like may be further added.

The interlayer films of the invention 1 and the invention 2 are composed of the (A) layer having excellent heat shielding properties, in which nanoscale ultrafine ITO particles smaller than the visible light wavelength are uniformly dispersed, and a viscosity average. By laminating the (B) layer or the (C) layer having excellent sound insulating properties in a wide temperature range using a resin whose degree of polymerization is adjusted, heat insulating property, sound insulating property, electromagnetic wave permeability, It has good penetration resistance, moisture resistance, transparency, particularly haze, and has an appropriate adhesive strength with glass, and can be obtained at low cost.

The method for forming the intermediate film of the first and second inventions is not particularly limited, and the film can be formed by, for example, an extrusion method, a calender method, a pressing method, or the like, but the biaxial extrusion method in the same direction is preferable. The haze can be further improved.

At least two (A) layers and (B) layer or (C) layer sandwiched between the above (A) layers.
In addition to the laminated structure of layers, (A) layer, (B)
A layer and an intermediate film other than the layer (C) may be laminated. Specifically, for example, an interlayer film formed by further laminating a (D) layer composed of a polyvinyl acetal resin (P) and a plasticizer (Z) is preferable, and is used as necessary for improving penetration resistance. . Such layers (A) and (B), and (C)
An intermediate film formed by laminating intermediate films other than the layers is also one aspect of the present invention. The plasticizer (Z) is not particularly limited, and may be the same as the plasticizer (W), the plasticizer (X), and the plasticizer (Y), for example.

A laminated glass in which the interlayer film of the present invention is interposed between at least a pair of glasses to be integrated is also one of the present invention. The glass is not particularly limited, and examples thereof include commonly used transparent plate glass and the like. It is preferably a heat ray absorbing glass having a transmittance of 65% or less in the entire wavelength range of 900 nm to 1300 nm. Since the infrared ray cutting effect of ITO is large on the longer wavelength side than 1300 nm and relatively small in the region of 900 nm to 1300 nm, by combining the interlayer film of the present invention with the heat ray absorbing glass as compared with the case of combining with clear glass, Even with the same visible light transmittance, the solar radiation transmittance can be lowered, and high heat shield properties can be obtained.

In the laminated glass of the present invention, the interlayer film of the present invention is interposed between at least a pair of glasses to be integrated, so that the heat insulating property, the sound insulating property, the electromagnetic wave transmitting property, the penetration resistance, and the moisture resistance are obtained. It has good transparency, especially haze, and has an appropriate adhesive strength with glass, and can be obtained at low cost.

[0101]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Example 1) <Synthesis of polyvinyl butyral resin> 2890 g of pure water
Then, 275 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 99.2 mol% was added and dissolved by heating. The temperature of this solution was adjusted to 15 ° C, and hydrochloric acid with a concentration of 35% by weight
01 g and n-butyraldehyde 157 g were added, and 15
The reaction product was precipitated by maintaining the temperature of ℃. Then, the reaction system is set to 6
The mixture was kept at 0 ° C for 3 hours to complete the reaction, washed with excess water to wash off unreacted n-butyraldehyde, hydrochloric acid was neutralized with an aqueous sodium hydroxide solution, and further washed with excess water.
After washing with water for an hour and drying, a polyvinyl butyral resin (hereinafter, also referred to as PVB) in the form of white powder was obtained. The degree of acetalization of this resin was 68.9 mol% and the amount of acetyl groups was 0.9 mol%.

<Preparation of ITO Dispersion Plasticizer> Triethylene glycol di-2-ethylhexanoate (hereinafter referred to as 3G
Also referred to as O), 0.63 parts by weight of ITO fine particles (manufactured by Mitsubishi Materials Corp.) was added to 39 parts by weight, and polyphosphoric acid ester salt was used as a dispersant, and the ITO fine particles were mixed in 3GO with a horizontal microbead mill. Dispersed. While stirring this dispersion, 0.1 part by weight of acetylacetone was added to obtain an ITO dispersion plasticizer. The average particle diameter of the ITO fine particles in the ITO dispersion plasticizer was 35 μm.

<Production of Membrane (A)> With respect to 100 parts by weight of PVB, 39 parts by weight of the ITO dispersion plasticizer,
An appropriate amount of magnesium ethylbutyrate so that the magnesium content is 60 ppm with respect to the entire system, 0.1 part by weight of Sumirider BHT (manufactured by Sumitomo Chemical Co., Ltd.) as an antioxidant,
2- (2'-hydroxy-3'-t as a UV absorber, etc.
-Butyl-5'-methylphenyl) -5-chlorobenzotriazole (manufactured by Ciba-Geigy, Tinuvin 3
26) was added and mixed in an amount of 0.1 part by weight. After thoroughly kneading this mixture with a mixing roll, use a press molding machine to
A film (A) having a thickness of 0.3 mm was produced by press molding at 0 ° C. for 30 minutes.

<Production of Membrane (B)> The viscosity average degree of polymerization is 20.
PVA having a viscosity average degree of polymerization of 3500 was added to and mixed with PVA of No. 00 at 50% by weight. PVB having an acetalization degree of 63.6 mol% and an acetyl group content of 14.3 mol% was synthesized from the mixed PVA. 60 parts of 3GO was added as a plasticizer to 100 parts by weight of the obtained PVB.
Parts by weight, magnesium 2-ethylbutyrate in an appropriate amount so that the magnesium content is 60 ppm with respect to the entire system, 0.1 parts by weight of Sumirider BHT (manufactured by Sumitomo Chemical Co., Ltd.) as an antioxidant, and a UV absorber, etc. 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole (Ciba Geigy, Ti
Nuvin 326) was added and mixed in an amount of 0.1 part by weight. After sufficiently melting and kneading this with a mixing roll, press molding with a press molding machine at 150 ° C. for 30 minutes to give a thickness of 0.1.
A 6 mm film (B) was prepared.

<Preparation of Intermediate Film> Using the two obtained films (A) and the film (B), the film (A) was prepared so that the film (A) / the film (B) / the film (A) was obtained. An intermediate film having a three-layer structure with the film (B) sandwiched therebetween was produced.

<Production of Laminated Glass> The obtained interlayer film was sandwiched by two pieces of float plate glass of 300 mm × 300 mm × thickness of 3 mm from both sides, and the unbonded sandwich was placed in a rubber bag. After degassing at a vacuum degree of 7 kPa for 20 minutes, transfer to a 90 ° C. oven in the degassed state,
Hold at this temperature for 30 minutes. The sandwiched body thus temporarily adhered by the vacuum press was then thermocompression bonded in an autoclave at a pressure of 1.2 MPa and a temperature of 135 ° C. to produce a transparent laminated glass.

Example 2 In the production of the film (A), I
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the amount of TO particles charged was 1.27 parts by weight with respect to 39 parts by weight of 3GO.

Example 3 In the production of the film (A), I
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the amount of TO fine particles charged was 2.53 parts by weight with respect to 39 parts by weight of 3GO.

Example 4 In the preparation of the film (A), I
The amount of TO fine particles charged was set to 1.27 parts by weight with respect to 39 parts by weight of 3GO, and PVB having an acetalization degree of 63.6 mol% and an acetyl group content of 14.3 mol% was used in the production of the film (B). Instead of being used, the viscosity average degree of polymerization is 200.
0 of PVA with a viscosity average degree of polymerization of 3500 is 30
The mixed PVA was added and mixed so that the weight% was obtained.
Thus, an interlayer film and a laminated glass were produced in the same manner as in Example 1 except that PVB having an acetalization degree of 63.3 mol% and an acetyl group amount of 14.3 mol% was synthesized and used.

Example 5 In the production of the film (A), I
The amount of TO fine particles charged was set to 1.27 parts by weight with respect to 39 parts by weight of 3GO, and PVB having an acetalization degree of 63.6 mol% and an acetyl group content of 14.3 mol% was used in the production of the film (B). Instead of using it, the viscosity average degree of polymerization is 170.
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that PVB having an acetalization degree of 64.5 mol% and an acetyl group content of 14.3 mol% was synthesized from PVA of 0. did.

Example 6 In the production of the film (A), I
The amount of the TO fine particles charged was 1.27 parts by weight with respect to 39 parts by weight of 3GO, and in the membrane (B), PVB having a degree of acetalization of 63.6 mol% and an amount of acetyl groups of 14.3 mol% was synthesized. Instead of mixing 60 parts by weight of 3GO as a plasticizer with 100 parts by weight of the obtained PVB, 100 parts by weight of PVA having a viscosity average degree of polymerization of 2300 and 42 parts by weight of PVA having a viscosity average degree of polymerization of 4000 were mixed. PVB having an acetalization degree of 57.3 mol% and an acetyl group content of 20.0 mol% was synthesized from the obtained PVA, and 4 GO was added as a plasticizer to 6 parts by weight of 4 GO with respect to 100 parts by weight of the obtained PVB.
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that 0 part by weight was mixed.

(Comparative Example 1) In the preparation of the film (A), I
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that TO particles were not added.

(Comparative Example 2) In the preparation of the film (A), I
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the amount of TO particles charged was 0.006 parts by weight with respect to 39 parts by weight of 3GO.

(Comparative Example 3) In the preparation of the film (A), I
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the amount of TO particles charged was 6.33 parts by weight with respect to 39 parts by weight of 3GO.

(Comparative Example 4) In the preparation of the film (A), I
The amount of TO fine particles charged was 1.27 parts by weight with respect to 39 parts by weight of 3GO, and in the production of the film (B), the degree of acetalization was 63.6 mol% and the amount of acetyl groups was 14.3 mol. % PVB, instead of PVA having a viscosity average degree of polymerization of 2000, PVA having a viscosity average degree of polymerization of 3500 was added and mixed so as to be 50% by weight, and the mixed PVA had an acetalization degree of 68. 0.5 mol%,
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that PVB having an acetyl group content of 0.9 mol% was synthesized and used.

Comparative Example 5 Example 5 was repeated except that, in the preparation of the membrane (B), 40 parts by weight of 3GH was mixed as a plasticizer instead of mixing 60 parts by weight of 4GO as the plasticizer.
An interlayer film and a laminated glass were produced in the same manner as in.

Comparative Example 6 In the preparation of the membrane (B), 100 parts by weight of PVA having a viscosity average degree of polymerization of 2300 was mixed with 42 parts by weight of PVA having a viscosity average degree of polymerization of 4000 to obtain an acetal. The degree of chemical conversion is 57.3 mol%,
A PVB having an acetyl group content of 20.0 mol% was synthesized, and 60 parts by weight of 4GO was mixed as a plasticizer with 100 parts by weight of the obtained PVB.
PVA having a degree of acetalization of 65.9 mol% and an amount of acetyl groups of 0.9 mol% was synthesized from PVA obtained by mixing 42 parts by weight of PVA having a viscosity average degree of polymerization of 4000 with 100 parts by weight of PVA. Then, an interlayer film and a laminated glass were produced in the same manner as in Example 6 except that 60 parts by weight of 3GH as a plasticizer was mixed with 100 parts by weight of the obtained PVB.

(Evaluation) With respect to the laminated glass produced in Examples 1, 2, 3, 4, 5, 6 and Comparative Examples 1, 2, 3, 4, 5, 6, the following items were evaluated and the results are shown. Is shown in Table 1.

(1) Optical characteristics Direct measurement A spectrophotometer (UV3100, manufactured by Shimadzu Corp.) was used to measure the transmittance of the laminated glass in the wavelength range of 300 to 2500 nm, according to JIS Z 8722 and JIS.
380 to 780 according to R 3106 (1998)
Visible light transmittance (Tv) in the wavelength region of nm, 300 to 2
The solar radiation transmittance (Ts) in the wavelength region of 500 nm was obtained.

(2) Haze (Hz) It was measured according to JIS K 6714.

(3) Dispersed state slicer in ITO intermediate film (Ultramicrotome Leica, E
M-ULTRACUT ・ S; FC-S type freezing cutting system Leica company made, REICHERT-NISSEI-F
CS; knife, DIATOME, DIATOME
ULTRA CRYO DRY) was used to prepare a thin piece of an intermediate film, and then a transmission electron microscope (H, manufactured by Hitachi, Ltd.)
-7100FA type, TEM), accelerating voltage 10
Photograph the area of 10μm × 10μm at 0kV
The dispersed state of O fine particles was observed. The particle diameter of the ITO fine particles was the longest diameter of the ITO fine particles in the photograph. The particle diameters of all the ITO fine particles in the above photographing range were measured, and the average particle diameter was determined by volume conversion average. In addition, the number of particles having a particle diameter of 100 nm or more existing in the photographing range is calculated and divided by a photographing area of 100 μm ² to obtain 1 μm ²
The number of particles having a particle diameter of 100 nm or more per particle was calculated.

(4) Electromagnetic Wave Transmissivity The reflection loss value (dB) in the frequency region of 0.1 to 10 MHz was measured by the near-field electromagnetic wave shielding effect measuring method (KEC method), and the thickness was usually 2.5 mm. It was compared with the value obtained from the float glass veneer. Further, as a method for measuring the electromagnetic shield effect in the far field, a laminated glass 600 mm square is set up between a pair of transmitting and receiving antennas, and the radio wave from the radio wave signal generating device is received by a spectrum analyzer to obtain 2 to 26.5 GHz. The reflection loss value (dB) in the frequency domain was measured and compared with the value obtained from a normal float glass veneer having a thickness of 2.5 mm. As a result of the comparison in the entire measurement frequency region, Table 1 shows the minimum value to the maximum value of the difference (ΔdB) between the two.

(5) Cloud Point 8 parts by weight of PVB used in the production of the film (B) were dissolved in 100 parts by weight of the plasticizer used in the production of the film (B) to obtain a solution. After heating the obtained solution to 150 ° C. or higher, 10
The temperature was lowered by leaving it in an atmosphere of -30 ° C, and the temperature at which part of the solution began to become cloudy was visually observed.

(6) Sound insulation properties At 0 ° C., 10 ° C., 20 ° C., and 30 ° C., laminated glass was subjected to a vibration generator for vibration damping test (vibratory shaker G21-005D, manufactured by Shinken Co., Ltd.). Excitation is performed, and the obtained vibration characteristics are amplified by a mechanical impedance amplifier (XG-81 manufactured by Rion Co.), and the vibration spectrum is FFT.
Analyzer (FFT manufactured by Yokogawa Hewlett-Packard Company)
It was analyzed by a spectrum analyzer HP-3582AA). The loss factor was calculated from the loss factor thus obtained and the ratio of the resonance frequency of the glass. Based on this result, the minimum transmission loss value near the frequency of 2000 Hz was set as the TL value.

(7) Measurement of dynamic viscoelasticity The laminate was sampled in a rectangle of 10 cm × 16 cm,
Solid viscoelasticity measurement device (Rheometrics, RSA-
Using II), a sine strain with a measurement frequency of 10 Hz was applied in the shear direction at a strain amount of 0.1% at a measurement temperature range of −20 ° C. to + 100 ° C. and a temperature rising rate of 3 ° C./min.
As the dynamic viscoelastic characteristics, the storage elastic modulus, the loss elastic modulus, and the loss tangent (tan δ) that is a ratio of these are measured, and the temperature indicated by the maximum value on the lowest temperature side is obtained from the obtained temperature curve of tan δ. It was

[0127]

[Table 1]

From Table 1, it can be seen that the laminated glass produced in Examples 1, 2, 3, 4, 5 and 6 has excellent heat insulating properties, sound insulating properties and transparency. The laminated glass produced in Comparative Examples 1 and 2 was inferior in heat shield property because it did not sufficiently contain ITO in the intermediate film. The laminated glass produced in Comparative Example 3 contained ITO in excess, and thus was inferior in transparency. The laminated glass produced in Comparative Examples 4, 5 and 6 was inferior in sound insulation because the amount of acetyl groups in PVB, the type of plasticizer and the like were not optimized.

[0129]

EFFECTS OF THE INVENTION According to the present invention, for laminated glass such as transparency, weather resistance, impact energy absorption, appropriate adhesion to glass capable of preventing plate misalignment and foaming, film physical properties, moldability, handleability, etc. Prevents the decrease in TL value by relaxing the coincidence effect without impairing the basic performance required for the interlayer film,
Moreover, it has excellent sound insulation in a wide temperature range, and IT
By having a layer in which O fine particles are uniformly dispersed, it is possible to obtain an interlayer film for laminated glass and a laminated glass having excellent heat shielding properties.

[Brief description of drawings]

FIG. 1 is a diagram showing the sound insulation of a general glass plate against frequency.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) C08K 5/00 C08K 5/00 9/02 9/02 C08L 29/14 C08L 29/14 F term (reference) 4F100 AA33A AA33B AA33C AA33H AK23A AK23B AK23C AL05B BA03 BA10A BA10C CA04A CA04B CA04C CA07A CA07B CA07C DE01A DE01B DE01C JA07B JD10 JN01 YY00B 4G061 AA02 AA04 AA11 AA21 AA28 BA01 BA02 CA02 CB03 CB12 CB18 CD02 CD18 DA23 DA38 DA46 4J002 BE061 DE097 EH036 EH046 EH056 EW046 FB077 FD026 FD207 GJ00

Claims (12)

[Claims] 1. An intermediate film for laminated glass having a laminated structure comprising at least three layers of (A) layer of two layers and (B) layer sandwiched between the (A) layer, The (A) layer is composed of a polyvinyl acetal resin (P), a plasticizer (W) and tin-doped indium oxide particles, and the (B) layer is composed of a polyvinyl acetal resin (Q) and a plasticizer (X). The tin-doped indium oxide particles have an average secondary agglomerated particle diameter of 80 in the layer (A).
nm or less and particles having a secondary aggregate particle diameter of 100 nm or more are dispersed in the (A) layer so as to have a density of 1 particle / μm ² or less, and the polyvinyl acetal is contained in the (A) layer. 0.01 to 100 parts by weight of resin (P)
To 3.0 parts by weight, the polyvinyl acetal resin (Q) has a viscosity average degree of polymerization of 1000 to 300.
The difference in viscosity average degree of polymerization between the polyvinyl acetal resin (R) of 0 and the polyvinyl acetal resin (R) is 15
00 or more and a viscosity average degree of polymerization of 3000 to 5000
Of polyvinyl acetal resin (S), and the degree of acetalization is 60 to 85 mol%, the amount of acetyl groups is 8 to 30 mol%, and the sum of the degree of acetalization and the amount of acetyl groups is 75 mol%. And above, the plasticizer (X)
100 parts by weight of the polyvinyl acetal resin (Q) 8
An interlayer film for laminated glass, wherein the cloud point of the solution in which parts by weight is dissolved is 50 ° C. or lower. 2. An intermediate film for laminated glass having a laminated structure comprising at least three layers of (A) layer of two layers and (C) layer sandwiched between the (A) layer, The (A) layer is composed of a polyvinyl acetal resin (P), a plasticizer (W) and tin-doped indium oxide particles, and the (C) layer is composed of a polyvinyl acetal resin (T) and a plasticizer (Y). The tin-doped indium oxide particles have an average secondary agglomerated particle diameter of 80 in the layer (A).
nm or less and particles having a secondary aggregate particle diameter of 100 nm or more are dispersed in the (A) layer so as to have a density of 1 particle / μm ² or less, and the polyvinyl acetal is contained in the (A) layer. 0.01 to 100 parts by weight of resin (P)
˜3.0 parts by weight, and the plasticizer (Y) is
At least selected from the group consisting of triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, triethylene glycol di-n-heptanoate, and tetraethylene glycol di-n-heptanoate. One kind,
In the temperature dependence of the loss tangent obtained from the dynamic viscoelasticity, the layer (C) has a maximum temperature of 3 at the lowest temperature.
An interlayer film for laminated glass, which is 0 ° C. or lower. 3. The combination according to claim 2, wherein the cloud point of a solution in which 8 parts by weight of the polyvinyl acetal resin (T) is dissolved in 100 parts by weight of the plasticizer (Y) is 50 ° C. or lower. Intermediate film for glass. 4. A polyvinyl acetal resin (T) 100.
4. The combination according to claim 2, wherein the blending amount of the plasticizer (Y) is 5 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin (P) with respect to 100 parts by weight of the polyvinyl acetal resin (P). Intermediate film for glass. 5. The polyvinyl acetal resin (T) has a viscosity average degree of polymerization of 1500 or more, an acetalization degree of 60 to 85 mol%, an acetyl group amount of 8 to 30 mol%, an acetalization degree and an acetyl group. The interlayer film for laminated glass according to claim 2, 3 or 4, wherein the total amount with the base amount is 75 mol% or more. 6. The polyvinyl acetal resin (T) comprises a polyvinyl alcohol resin (G) and a polyvinyl alcohol resin (H) having a viscosity average polymerization degree difference of 500 or more with the polyvinyl alcohol resin (G). It is obtained from polyvinyl alcohol resin (I),
And the degree of acetalization is 60 to 85 mol%, the amount of acetyl groups is 8 to 30 mol%, and the sum of the degree of acetalization and the amount of acetyl groups is 75 mol% or more. The interlayer film for laminated glass according to 4 or 5. 7. The polyvinyl alcohol resin (G) has a viscosity average degree of polymerization of 500 to 3,000, and the polyvinyl alcohol resin (H) has a viscosity average degree of polymerization of 3,000 to 3,000.
It is 5000, The interlayer film for laminated glasses of Claim 6 characterized by the above-mentioned. 8. The polyvinyl acetal resin (T) comprises a polyvinyl acetal resin (U) and a polyvinyl acetal resin (V) having a difference in viscosity average degree of polymerization between the polyvinyl acetal resin (U) and 500 or more. The degree of acetalization is 60 to 85 mol%, the amount of acetyl groups is 8 to 30 mol%, and the sum of the degree of acetalization and the amount of acetyl groups is 75 mol% or more. The interlayer film for laminated glass according to 2, 3, 4 or 5. 9. The polyvinyl alcohol resin (U) has a viscosity average degree of polymerization of 500 to 3,000, and the polyvinyl alcohol resin (V) has a viscosity average degree of polymerization of 3,000 to 3,000.
The interlayer film for laminated glass according to claim 8, which is 5,000. 10. A polyvinyl acetal resin (P), a polyvinyl acetal resin (Q), a polyvinyl acetal resin (R), a polyvinyl acetal resin (S), a polyvinyl acetal resin (T), a polyvinyl acetal resin (U) and / or a polyvinyl acetal resin. Acetal resin (V) is
It is polyvinyl butyral resin, The intermediate film for laminated glasses of Claim 1, 2, 3, 4, 5, 6, 7, 8 or 9. 11. A laminate of (D) layers comprising a polyvinyl acetal resin (P) and a plasticizer (Z), which are laminated.
The interlayer film for laminated glass according to 7, 8, 9 or 10. 12. An interlayer film for laminated glass according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 is interposed between at least a pair of glasses to be integrated. Laminated glass characterized by becoming.